TW412762B - Ceramic multilayer capacitor - Google Patents
Ceramic multilayer capacitor Download PDFInfo
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- TW412762B TW412762B TW087119799A TW87119799A TW412762B TW 412762 B TW412762 B TW 412762B TW 087119799 A TW087119799 A TW 087119799A TW 87119799 A TW87119799 A TW 87119799A TW 412762 B TW412762 B TW 412762B
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- 239000003990 capacitor Substances 0.000 title claims abstract description 49
- 239000000919 ceramic Substances 0.000 title claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 27
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 13
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 12
- 229910052788 barium Inorganic materials 0.000 claims abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 6
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 5
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 5
- 239000011159 matrix material Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000007650 screen-printing Methods 0.000 claims description 5
- 239000002075 main ingredient Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 238000003980 solgel method Methods 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 1
- 238000009413 insulation Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229910052689 Holmium Inorganic materials 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 31
- 229910010293 ceramic material Inorganic materials 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000011575 calcium Substances 0.000 description 12
- 238000005245 sintering Methods 0.000 description 11
- 239000000843 powder Substances 0.000 description 9
- 239000010408 film Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000003989 dielectric material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910005883 NiSi Inorganic materials 0.000 description 1
- 241000282330 Procyon lotor Species 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 206010039722 scoliosis Diseases 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052861 titanite Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
- H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
Landscapes
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Ceramic Capacitors (AREA)
Abstract
Description
412762 五、發明說明(1) 本發明係關於一種包含以摻雜型(Ba, Ca)[Ti, Zr]〇3為基 質上之多層陶瓷層以及多層之Ni製電極層之陶瓷多層電容 器,陶瓷層與電極層相互交疊而形成之多層結構之兩側面 均有電連接1而且該電連接接達了諸多電極層。本發明亦 關於適用在陶瓷多層電容器之陶瓷材料。本發明更關於製 造陶瓷多層電容器之方法° 前言述及之此種陶瓷多層電容器眾所皆知。美國專利文 件第US 5 , 3 1 9 , 5 1 7即有詳述。此專利揭示者,更詳細言 之,即一種多層電容器,其陶瓷層以摻雜型 (Ba, Ca,Sr)[Ti,Zr]03為主要之基質材料。此材料即所謂 之妈鈦礦結構3就此材料而言,定量之Ca離子與Sr擊子取 代了鈣鈦礦中之Ba之位置(所謂A-位置),以及定量之Zr齬 子取代了 Ή之位置(所謂B -位置)。熟知電容器之電極層主 要由Ν 1製成。電容器之製造過程中,摻雜物質包括金屬 .Μη,Υ,V以及W及/或化合物於燒成時均會轉變成彼等之 氧化物型態而添加入經過徵燒以及粉碎後之 (B a, C a,S r ) [ T i,Z r ] 03粉末a為了降低陶瓷材料之最低燒 結溫度亦可加入燒結助劑=燒結溫度一定要相當低方可避 免Ni製電極層於燒結過程中熔融掉》 熟知之陶瓷多層電容器有一項缺點=掌已發現,實作 上,依指定之組成製成之電容器性能未臻最佳程度。尤其_ 是業已證明藉由熟知之電容器始終無法達成提昇電容器壽 命之要求。 本發明之一目的係改善上述之缺點。更詳細言之,本發412762 V. Description of the invention (1) The present invention relates to a ceramic multilayer capacitor including a multilayer ceramic layer with a doped (Ba, Ca) [Ti, Zr] 〇3 substrate and a multilayer electrode layer made of Ni. Both sides of a multilayer structure formed by overlapping layers and electrode layers have electrical connections 1 and the electrical connections reach a number of electrode layers. The invention also relates to ceramic materials suitable for use in ceramic multilayer capacitors. The present invention is more about a method of manufacturing a ceramic multilayer capacitor. Such ceramic multilayer capacitors are well known in the introduction. US Patent Documents Nos. 5, 3, 19, 5 1 7 are described in detail. The patent revealer, in more detail, is a multilayer capacitor whose doped (Ba, Ca, Sr) [Ti, Zr] 03 ceramic layer is the main matrix material. This material is the so-called mother titanite structure. 3 As far as this material is concerned, the quantitative Ca ions and Sr hammers replaced the position of Ba in the perovskite (the so-called A-position), and the quantitative Zr raccoon replaced Ή Location (so-called B-location). It is well known that the electrode layer of a capacitor is mainly made of N1. In the manufacturing process of capacitors, the doping materials include metals. Mn, rhenium, V, and W and / or compounds will be transformed into their oxide forms during firing and added to the burned and crushed (B a, C a, S r) [T i, Z r] 03 powder a In order to reduce the minimum sintering temperature of the ceramic material, a sintering aid can also be added = the sintering temperature must be quite low to avoid the Ni electrode layer in the sintering process There is a disadvantage of the well-known ceramic multilayer capacitors = the palm has found that, in practice, the performance of capacitors made according to the specified composition is not optimal. In particular, it has been proven that with the well-known capacitors, the requirements for improving the life of capacitors have never been achieved. An object of the present invention is to improve the above disadvantages. In more detail, this post
冥7頁 412762 五、發明說明(2) 明係旨在提出一種包含Ni製電極層之陶瓷多層電容器,係 具有很長之壽命,很高之介電常數,很高之絕緣電阻以及 理想之溫度特性。本發明亦應可提出一種可製成具備非常 長壽命、非常高之介電常數,非常高之絕緣電阻以及理想 之溫度特性之電容器之陶瓷材料。本發明之再一目的係提 出一種製造具有很長之壽命、非常高之介電常數,非常高 之絕緣電阻以及理想之溫度特性之陶瓷多層電容器之方 法。 本發明之此等以及其目的係以前言述及之該種陶瓷多層 電容器來達成,其他特點係摻雜型(Ba, Ca) [Ti , Zr ]03之主 要成f分之組成配方為· (Bat^CaJCTi^a^^Zr^MObA^'A-o 其中:0 . 0 0 S X S 0 . 0 5 0.10 ^ y ^0.25 0.00 < a S 0.01 0.00 < b 0.01 0.00 ^ c ^0.01 0. 99 < k < 0.999 以及其中A代表包含丫, Ho, Dy, Er, Yb, Ga, Ni, Mg, Zn 以及A丨之系列中選出之至少一種元素。 許多實驗結果中1使得本發明得以成功,本發明者業發Page 7 412762 5. Description of the invention (2) The Ming system aims to propose a ceramic multilayer capacitor containing an electrode layer made of Ni. It has a long life, high dielectric constant, high insulation resistance, and ideal temperature. characteristic. The invention should also provide a ceramic material that can be made into a capacitor with a very long life, a very high dielectric constant, a very high insulation resistance, and ideal temperature characteristics. Still another object of the present invention is to provide a method for manufacturing a ceramic multilayer capacitor having a long life, a very high dielectric constant, a very high insulation resistance, and ideal temperature characteristics. These and other objects of the present invention are achieved by the ceramic multilayer capacitor mentioned in the introduction, and other characteristics are the main f component composition formula of doped type (Ba, Ca) [Ti, Zr] 03 as ( Bat ^ CaJCTi ^ a ^^ Zr ^ MObA ^ 'Ao where: 0. 0 0 SXS 0. 0 5 0.10 ^ y ^ 0.25 0.00 < a S 0.01 0.00 < b 0.01 0.00 ^ c ^ 0.01 0. 99 < k < 0.999 and A represents at least one element selected from the series consisting of Y, Ho, Dy, Er, Yb, Ga, Ni, Mg, Zn, and A 丨. Among many experimental results, 1 makes the present invention successful. Inventor
第8頁 412762 五、發明說明(3) 現對上述型態之電容器進行極快加速壽命試驗(HALT)證明 壽命出乎意料的延長而且可靠度很高。再者,亦證明本發 明之電容器具有很高之介電常數ε (1 5,0.0 0且更高),相當 低之損失因子(5 %或更低)以及相當高之絕緣電阻。第一組 實驗證明介電常數與溫度之關係〇溫度特性)符合Ε I Α所謂 之Y5V標準。 目前對壽命很長之原因仍不明瞭。不過本發明者深信複 雜之Μη-Μό錯合物是本項優良效應之主因。咸認為此種施 體/受體-錯合物可避免介電材料之晶粒之BaTi 03結構中 所謂0空位之形成。已知此種0-空位之存在會降低介電材 料之絕緣電阻 '而使陶瓷多層電容器之壽命大減。上述提 及之施體/受體錯合物會形成極強之應力中心,而使0 -空 位之移動率降低。W及/或V之存在對此種錯合物之形成或 存在有不良之影響,因而造成誠如US 5, 319,51 7所示者, 導致壽命大為降低。Page 8 412762 V. Description of the invention (3) The extremely fast accelerated life test (HALT) of the capacitor of the above type is now conducted to prove that the life is unexpectedly extended and the reliability is very high. Furthermore, it has been proved that the capacitor of the present invention has a high dielectric constant ε (15, 0.0 and higher), a relatively low loss factor (5% or lower), and a relatively high insulation resistance. The first set of experiments proved that the relationship between dielectric constant and temperature (temperature characteristics) meets the so-called Y5V standard of EI. The cause of the long life is still unknown. However, the inventors are convinced that the complex Mη-Μό complex is the main cause of this excellent effect. It is believed that such donor / acceptor-complexes can avoid the formation of so-called zero vacancies in the BaTi 03 structure of the grains of the dielectric material. It is known that the existence of such a 0-vacancy will reduce the insulation resistance of the dielectric material and greatly reduce the life of the ceramic multilayer capacitor. The donor / acceptor complexes mentioned above will form extremely strong stress centers, which will reduce the 0-vacancy mobility. The presence or absence of W and / or V has an adverse effect on the formation or existence of this complex, and as a result, as shown in US 5,319,51 7, the life span is greatly reduced.
BaT 1 03晶體結構中加入摻雜物質係使本發明材料適於充 當陶瓷多層電容器中之介電材料之必要條件。本例中,C a 離子佔據B a或受Μ位置,而Z r,Μ η以及Z r,Μ η以及N b離子 則佔據了 BaT 1 03材料中之T 1或施體位置。請注意摻雜物質 之指定量之計算方式係以佔據在材料中之全部有效Ba以及 T i之位置之份量計之。 指定量令位在陶瓷材料之B a位置上之C a存量被視為致使 陶瓷多層電容器運作良好.之主因。C a之存量使陶瓷材料之 介電峯變寬3陶瓷材料内Ca為量超過0. 0 5之份量時使得材The addition of a dopant substance to the BaT 1 03 crystal structure is necessary to make the material of the present invention suitable for use as a dielectric material in ceramic multilayer capacitors. In this example, the Ca ion occupies the Ba or M position, and the Z r, M η and Z r, M η, and N b ions occupy the T 1 or donor position in the BaT 1 03 material. Please note that the specified amount of the doping substance is calculated in terms of the amount of all effective Ba and T i positions in the material. The specified amount of C a stock at the B a position of the ceramic material is considered to be the main reason that makes the ceramic multilayer capacitor work well. The amount of C a widens the dielectric peak of the ceramic material. 3 The amount of Ca in the ceramic material exceeds 0.5 5
412762 五、發明說明(4) 料之介電數降至極低值3再者,若X > 0 . Q 5時則介電損失益 形嚴重=若陶瓷材料内Ba位置上之Ca存量範圍介於0. 03以 及0. 0 4 5之份量則就儘量避免之小介電峯以及因為高介電 損失之低介電常數兩者之間而言可獲致最佳調適。 指定量中位在陶瓷材料内之T 1位置上之Zr 1 Mn,Mo以及 元素A之存量亦被視為致使陶瓷多層電容器運作良好之主 要先決條件。就其它摻雜物質而言,Zr之存量導致BaT 1 03 之介電常數居圼點之最大值偏移阜高溫區。若Zr量低於0. 1之份量或高於0. 2 5之份量時,則居里點分別不是太低就 是太高。如此使得材料在操作溫度室溫)下之介電常數 太低。若Zr量範圍介於0. 17以及0. 22之份量之間,則居里 點之位置位於最佳點。 Μη在根據本發明之多層電容器之陶瓷材料之燒結中扮演 很重要之角色。燒結製程在還原氣份中進行。在燒結過程 中,β a T i 0 3,可能會被還原。如此得使燒結方法製成之陶 瓷材料之阻抗性大打折扣,並使多層電容器之壽命減低。 ’這是最不願樂見的*實驗中已證實若陶瓷材料内之Ti位置 上有定量Μη之存在可免陶瓷材料發生不樂見到之特性衰 減。Μη之效能可防止還原現象發生,尤其是在陶瓷材斜中 之晶粒内。若陶瓷材料中内含Μ η量超過0 . 0丨之份量,則介 電常數過低。在期望特性之間獲致之最佳條件,係當Μη量 範圍介於0 . 0 0 2以及0 . 0 0 6之份量之間之際,則可避免封斜 之還原以及獲得高介電常數= 誠如前述〗Mo之存量亦很重要,尤其是對Mo以及Μη之間412762 V. Description of the invention (4) The dielectric number of the material is reduced to an extremely low value of 3, and further, if X > 0. Q 5, the dielectric loss is severely beneficial = if the Ca content range at the Ba position in the ceramic material The weights of 0.03 and 0.04 5 are optimally adjusted between the small dielectric peaks to be avoided and the low dielectric constant due to high dielectric loss. The presence of Zr 1 Mn, Mo and element A in the specified amount at the T 1 position in the ceramic material is also considered as the main prerequisite for the good operation of ceramic multilayer capacitors. As for other doping substances, the presence of Zr causes the maximum value of the dielectric constant of BaT 103 to shift from the high temperature region of Fu. If the amount of Zr is lower than the portion of 0.1 or higher than the portion of 0.25, the Curie points are either too low or too high, respectively. This makes the dielectric constant of the material too low at operating temperature (room temperature). If the Zr amount range is between 0.17 and 0.22, the position of the Curie point is at the best point. Mη plays an important role in the sintering of the ceramic material of the multilayer capacitor according to the present invention. The sintering process is performed in a reducing gas. During the sintering process, β a T i 0 3 may be reduced. In this way, the resistance of the ceramic material made by the sintering method is greatly reduced, and the life of the multilayer capacitor is reduced. ‘This is the least desirable. * It has been proven in experiments that the presence of a certain amount of η at the Ti position in the ceramic material prevents the ceramic material from undesirably deteriorating its characteristics. The effectiveness of Mn can prevent the reduction phenomenon, especially in the crystal grains in the ceramic material. If the amount of M η contained in the ceramic material exceeds 0.0 丨, the dielectric constant is too low. The best conditions obtained between the desired characteristics are when the amount of Mη ranges between 0.02 and 0.06, so that the reduction of the sealing can be avoided and a high dielectric constant can be obtained = As mentioned above, the amount of Mo is also very important, especially for Mo and Mη.
第10頁 412762 五、發明說明(5) 複雜之施體-受體錯合物之形成而言。咸信此等錯合物係 本發明多層電容器具有非常長之壽命之原因。極少量之 Μ 〇,即約0 . 0 0 1之份量則可延長電容器之工作壽命。業已 證實若該材料内之Mo量遠超過0. 0 1之份量時則介電材料趨 向於更具半導電性。Mo量之較佳值範圍介於0. 0 0 2以及 0. 0 0 6 5之份量之間1旨在使介電材料之高工作壽命以及不 期望之半導電特性之間獲致最佳之組合。注意Mo量最好高 於Μη以及A之總量。 較佳情況係,本發明多層電容器之摻雜型 (:83,〇&)[1'1,2]^03亦含有少量選自包含丫,}1〇)0火£1% Y b, G a, N i, M g, Ζ η以及A 1芩系列中之一種或更多種元 素。此等元素具有固定之價數。此等元素加入後,溫度特 性之最佳化,介電常數以及其它所要求之特性均可達成。 不過,此等元素之總量之最大量應為0. 0丨之份量。若使兩 量超過0. 0 1之份量,則會在介電材料内生成非期望相最佳 量範圍介於0 . 0 0 2以及0 . 0 0 6之份量。實驗之已發現,較特 別的是Y,Ga及/或Zn之存量對本發明之多層電容器之壽 命有正面之影響。 甴於鈣鈥礦結構内(k值不等於零)之(置換型)了 1原子以 及(置換型)Ba原子之數量不等,所以0原子之數量並不剛 好為3。公式内偽離3之量以(5代表之。因為受體原子之數 量超過施體原子之數量,所以原來應該於材料内出現之0 原子之位置則甴形成之空位取代了。 •本發明係亦關於一種以摻雜型(Ba, Ca)[Ti,Zr]03為基質Page 10 412762 V. Description of the invention (5) In terms of the formation of complex donor-receptor complexes. It is believed that these complexes are the reason why the multilayer capacitor of the present invention has a very long life. A very small amount of M0, that is, a portion of about 0.01 can extend the working life of the capacitor. It has been confirmed that the dielectric material tends to be more semiconductive if the amount of Mo in the material is far more than 0.01 parts. The preferred range of Mo amount is between 0. 0 2 and 0. 0 6 5 1 The purpose is to achieve the best combination between the high working life of the dielectric material and the undesired semiconducting properties . Note that the amount of Mo is preferably higher than the total amount of Mn and A. Preferably, the doped type (: 83, 〇 &) [1'1,2] ^ 03 of the multilayer capacitor of the present invention also contains a small amount selected from the group consisting of y,} 1〇), and 1% Y b, One or more elements in the G a, N i, M g, Z η and A 1 芩 series. These elements have a fixed price. After the addition of these elements, the optimization of temperature characteristics, dielectric constant and other required characteristics can be achieved. 0 丨 的 份量。 However, the maximum amount of the total of these elements should be 0. 0 丨 的 份量. If the amount is more than 0.01 parts, the optimal amount of the undesired phase in the dielectric material will be in the range of 0.02 and 0.06. It has been found through experiments that, more specifically, the amount of Y, Ga, and / or Zn has a positive effect on the life of the multilayer capacitor of the present invention. The number of (replacement type) 1 atoms and (replacement type) Ba atoms in the calcium 'ore structure (k value is not equal to zero) varies, so the number of 0 atoms is not exactly 3. The amount of pseudo 3 in the formula is represented by (5. Because the number of acceptor atoms exceeds the number of donor atoms, the positions of the 0 atoms that should originally appear in the material are replaced by vacancies. • The present invention is Also about a doped (Ba, Ca) [Ti, Zr] 03 matrix
第11頁 412762 五、發明說明(6) 之新穎之陶瓷组成。根據本發明,此組成之特點係主要成 份之組成配方為 (Ba,. Ζτγ\ foaMobAc)k03-5 其 中 * 0.00 ^ X 0.05 0.10 ^ y 0.25 0.00 < a 0.01 0.00 < b 0.01 0.00 ^ c 0. 01 0. 99 < k < 0.999 以 及 其 中A代表i i i ΐ包含Y, Ho ,Dy Ϊ Er > Yb 5 Ga ,Νι, Mg j Zn 以及A i之 系 列 中之至 少 一種 元 素 〇 此 配 方之陶瓷 组 成 可製成 絕 佳之 陶 瓷 容 哭 σσ j 尤其是 包 含Νι 制 衣 電極層之 陶 瓷 多層電 容 态° 此 種 極 層 之 金屬含 量 有 5 少 9 0 w t % ^較佳者為至少9 8 \v t % 之 Νι 0 基 於 上述理 甴 1 亦 最好應用 以 下 配方=0, .0 3 ^ X <; 0. 45 ; 0. 17 ^ y ^ 0.22 ; 0 . 0 0 2 < a ^ 0 . 0 0 6 ; 0 . 0 0 2 <b ^ 0 . 0 0 6 5 ; 0. 0 0 2 Sc S 0 . 0 0 6以及0 . 9 9 < k < 0 , 9 9 9。較佳情況係A係代表Y,G'a以及 或者Zn a 本發明亦關於製造陶瓷多層電容器之方法,其中以摻雜 型(Ba, Ca)[Ti,Ζγ]03為基質之陶瓷薄膜係以Ni為主成份之 網版印刷電極層覆蓋之,隨後陶瓷層以及電極層交互堆疊Page 11 412762 5. The novel ceramic composition of invention description (6). According to the present invention, the characteristic of this composition is that the composition formula of the main ingredients is (Ba ,. ττγ \ foaMobAc) k03-5 where * 0.00 ^ X 0.05 0.10 ^ y 0.25 0.00 < a 0.01 0.00 < b 0.01 0.00 ^ c 0 01 0. 99 < k < 0.999 and where A represents iii ΐ contains Y, Ho, Dy Ϊ Er > Yb 5 Ga, Ni, Mg j Zn, and at least one element in the series A i. Ceramic composition can make excellent ceramic capacity σσ j, especially ceramic multilayer capacitor state containing Nim clothing electrode layer ° The metal content of this electrode layer is 5 less 9 0 wt% ^ The better is at least 9 8 \ 0% based on the above-mentioned principle 1 is also best to use the following formula = 0, .0 3 ^ X <;0.45; 0. 17 ^ y ^ 0.22; 0. 0 0 2 < a ^ 0. 0 0 6; 0. 0 0 2 < b ^ 0. 0 0 6 5; 0. 0 0 2 Sc S 0. 0 0 6 and 0.9 9 < k < 0, 9 9 9. A preferred case is that A represents Y, G'a, and or Zn a. The present invention also relates to a method for manufacturing a ceramic multilayer capacitor, in which a doped (Ba, Ca) [Ti, Zγ] 03-based ceramic thin film is based on The screen printing electrode layer with Ni as the main component is covered, and then the ceramic layer and the electrode layer are alternately stacked.
第12頁 412762 五、發明說明(了) 而形成一種多層結構,接著於還原之氣氛中煅燒並燒結, 此後對多層結構進行電連接,即連接多層電極層,其特點 係捧雜型(Ba,Ca)[Ti,Zr]03之主要成份之組成配方為: (Ba 卜 xCax) (Ti pa—b_c_yZryMnaMobAc)kO“ 其中:Ο . Ο 0 S x S Ο . Ο 5 0.10 ^ y ^0.25 0.00 < a ^ 0.01 0.00 < b ^0.01 0. 00 Sc ^ 0.01 0. 99 < k < 0.999 以及其中A代表選自包含Y, Ho, Dy, Er, Yb, Ga, Ni, M g, Z n以及A丨之系列中之至少一種元素。 誠如上述,根據本發明之多層電容器具有非常長之壽 命,很高之介電常數,很高之絕緣電阻以及理想之溫度特 性。尤其是當A為Y,Ga及/或Zn時更為適用。 本發明之第一較佳之優良具體實施例之特點係摻雜型 (Ba, Ca)[Ti, Zr]03之製備乃甴混合氧化物及/或所罔金屬 之碳酸鹽繼以煅燒以及研磨此混合物而成。摻雜型 (B a, C a ) [ Τ_ 1 , Z r ϊ Ο 3結構包含M a ’ Μ 〇以及一視需要一則煅燒 過程中摻雜物質Α將在Β之位置上彤成。因此該摻雜物質可 有陶瓷層之主成份之晶粒中均勻迠分佈。燒結助劑之採Page 12 412762 5. Description of the invention (formed) to form a multilayer structure, then calcined and sintered in a reducing atmosphere, and then electrically connect the multilayer structure, that is, to connect multiple electrode layers, its characteristics are heterotype (Ba, The composition of the main ingredients of Ca) [Ti, Zr] 03 is: (Ba xxCax) (Ti pa—b_c_yZryMnaMobAc) kO “where: 〇. 〇 0 S x S 〇. Ο 5 0.10 ^ y ^ 0.25 0.00 < a ^ 0.01 0.00 < b ^ 0.01 0. 00 Sc ^ 0.01 0. 99 < k < 0.999 and wherein A represents a member selected from the group consisting of Y, Ho, Dy, Er, Yb, Ga, Ni, M g, Z n And at least one element in the series of A 丨. As mentioned above, the multilayer capacitor according to the present invention has a very long life, a high dielectric constant, a high insulation resistance, and ideal temperature characteristics. Especially when A is Y, Ga and / or Zn are more applicable. The characteristics of the first preferred embodiment of the present invention are doped (Ba, Ca) [Ti, Zr] 03. The preparation is a mixed oxide and / or The carbonate of the metal is then calcined and ground the mixture. Doped (B a, C a) [Τ_ 1, Z r ϊ Ο 3 structure package Containing M a 'M 0 and if necessary, a doping substance A will be formed at the position of B during the calcination process. Therefore, the doping substance may have a uniform ytterbium distribution in the grains of the main component of the ceramic layer. Sintering aid Admiration
第13頁 412762 五、發明說明(8) 用,較佳者為S i 02 ’而混合物内之含量為0 . 1 ~丨.0 w t %較 佳,因為會使混合物具—備較佳之燒結特性。 本發明之'另一較佳之優良具體實施例之特性係摻雜型 (B a, C a ) [ T i,Z r ] 03係以溶膠一凝膠法製備而成'本發明方 法之本具體實施例中,首先製備一種内含有固相顆粒之膠 體懸浮液之有機溶液。在本例中,較佳者為利闻一種内含 水合之金屬烧氧化顆.粒之有機溶劑(例如,乙醇)。加入少 量水之後(以部伶酸或氫氧化物當作催化劑),金屬燒氧化 物即發生水合作闬。隨後聚縮合而成為所需之摻雜型(Ba, Ca ) [ T 1,Ζι· ] 03,此反應通常在提高懸浮液溫度後完成。最 後,去除溶劑,例如,利用蒸發之方式=因此獲得之摻雜 型(B a, C a ) [ T i, Z r ] 03展現出材料内之撞、雜物質到達最均勻 之分佈方式9 本發明之此等以及其它方面參酌下文所述之具體實施例 即可一目了然=圖示如下: 圖1為根據本發明之電容之圖示截面圖。 應注意,為明瞭起見,圓内之各部份未依比例缯'示。 圖1所示作根據本發明之多層電容器·-本電容器包含許 多以摻雜型(B a, C a ) [ T 1,Z r ] 03為基質之陶瓷層1。正確组 成係(BahCaxXTik-b-c-yZq.MnaMcvWOw ’其中0.00 SxS 0.05 ; 0. 1 0 ^ y ^ 0. 2 5 ; 0. 00<a ^ 0 . 0 1 ; 0. 00<b ^0. 01 ; 0 . 0 0 0 ^ c S 0 . 0 1以及0 . 9 9 < k < 0 . 9 9 9 ,而且其中A代表選自 含有 Υ , Η 〇, D y , E r, Y b, G a , N i , M g, Ζ η 以及 A 1 之系列 中之至少一種元素。Page 13 412762 V. Description of the invention (8) It is better to use Si 02 'and the content in the mixture is preferably 0.1 to 丨. 0 wt%, because it will make the mixture have better sintering characteristics. . The characteristic of another preferred embodiment of the present invention is the doped type (B a, C a) [T i, Z r] 03 is prepared by the sol-gel method. In the examples, an organic solution of a colloidal suspension containing solid phase particles is first prepared. In this example, the organic solvent (e.g., ethanol) containing hydrated metal oxide particles is preferred. After a small amount of water is added (using mediconic acid or hydroxide as a catalyst), the metal burns the oxide to undergo hydration. Subsequent polycondensation becomes the desired doped type (Ba, Ca) [T 1, Zι ·] 03. This reaction is usually completed after increasing the temperature of the suspension. Finally, the solvent is removed, for example, the evaporation method = the doped type (B a, C a) [T i, Z r] 03 thus obtained shows the collision in the material and the most uniform distribution of the impurities These and other aspects of the invention can be seen at a glance with reference to the specific embodiments described below. The diagram is as follows: FIG. 1 is a diagrammatic sectional view of a capacitor according to the present invention. It should be noted that for clarity, the parts within the circle are not shown to scale. The multilayer capacitor shown in Fig. 1 according to the present invention is composed of a plurality of ceramic layers 1 having a doped type (B a, C a) [T 1, Z r] 03 as a matrix. Correct composition system (BahCaxXTik-bc-yZq.MnaMcvWOw 'Where 0.00 SxS 0.05; 0. 1 0 ^ y ^ 0. 2 5; 0. 0 < a ^ 0. 0 1; 0. 0 < b ^ 0. 01; 0. 0 0 0 ^ c S 0. 0 1 and 0.9 9 < k < 0.9 9 9, and wherein A represents a member selected from the group consisting of Υ, Η 〇, D y, E r, Y b, G at least one element in the series of a, Ni, Mg, Zη and A1.
第14頁 五、發明說明(9) 電容器亦包含主要由Ni製之 具有兩側電适接3 '在不例中 止。此等連接含有一種焊料, 係利同網版印刷之方法而疊附 諸多網版印刷成之薄膜則可堆 膜堆疊後則繼之之電極層與一 之g 少臂電極層2 =此外電容器 ^位在電容器之相對兩側 例如銅。在實作中,電極層 f陶瓷薄膜上,此後,此等 登成。如圖所示,係陶瓷薄 層或其他電連接交替連接 為明瞭起見)圖1中僅示出6層雷 ❻I極層。實作中’陶究多 層電容器至少包含十層以及至多數 百層電極層。彼等厚度 一般介於約0. 5至2. 0微米之間。陶咨 n n a ^ ^ 」瓦缚犋之厚度一般介於 2至20微米之間=實作中’電容器係於堆疊成之經是網印 之薄膜之上下端加上-層覆蓋層4。覆蓋層一般由多居之 未經網印之陶究薄膜組成’而且係於經過網印之薄膜在堆 疊過程中夾入疊層中a 根據+發明之陶尤多層電谷fg也可完成,係利用習用之 氧化物/碳酸鹽法(第一種方法)’或溶膠〜凝膠法(苐二種方 法)為之3 第一種方法中’粉末混合物之製備係將具有指定組成之 定量所須金屬之氧化物及/或碳致鹽混合而得。為了製備 本發明之陶瓷材料,採罔之啟始材料如:Page 14 V. Description of the invention (9) The capacitor also includes a capacitor made mainly of Ni, which has an electrical connection on both sides of 3 '. These connections contain a solder, which is the same as the screen printing method, and the film printed with a lot of screen printing can be stacked, followed by an electrode layer and a g-arm electrode layer 2 = In addition capacitor ^ Located on opposite sides of the capacitor, such as copper. In practice, the electrode layer f is on a ceramic thin film, and thereafter, they are completed. As shown in the figure, ceramic thin layers or other electrical connections are alternately connected for the sake of clarity.) Figure 1 shows only 6 layers of thunder poles. In practice, a 'multilayer capacitor' contains at least ten and at most hundreds of electrode layers. Their thickness is generally between about 0.5 to 2.0 microns. Tao Shi n n a ^ ^ "The thickness of the tile tie is generally between 2 and 20 microns = in practice" The capacitor is stacked on top and bottom of the screen-printed film plus a -layer cover layer 4. The covering layer is generally composed of a multi-layered non-screen printed ceramic film 'and the screen-printed film is sandwiched into the stack during the stacking process. Using the conventional oxide / carbonate method (the first method) or the sol ~ gel method (the two methods) is the third method. In the first method, the preparation of the powder mixture is required for the quantitative determination of the specified composition. Metal oxides and / or carbon salts are obtained by mixing. In order to prepare the ceramic material of the present invention, the starting materials for mining are as follows:
BaCo:3(SABED)、CaC03( Merck ρ· a.)、Ti〇2 (FUji)、BaCo: 3 (SABED), CaC03 (Merck ρ · a.), Ti〇2 (FUji),
Zr02 (Mel )、MnC03( Baker)、M〇03( Merck)、a l2〇,( Merck )、Zr02 (Mel), MnC03 (Baker), M〇03 (Merck), a 120, (Merck),
Ga3 03 (Merck- Schuchardt) j (CH3COOH),Mg. 4H,0(Mer ck) 1 N i 0,Y2 03 (S ΐ a r c k ),Z n (i\l e r c k )以及 R E2 〇3 ( r e 代表 E r,D y,Ga3 03 (Merck- Schuchardt) j (CH3COOH), Mg. 4H, 0 (Mer ck) 1 N i 0, Y2 03 (S ΐ arck), Z n (i \ lerck), and R E2 〇3 (re represents E r, D y,
苐15頁 412762 五、發明說明CIO) Η 〇以及Y b ; A u e r - R e m y )。啟始材料之平均晶粒尺寸低於1 微米3 因此得到之粉末混合物係懸浮於水性溶液之内,而且其 中加入少量之分散劑1懸浮物利用Zr02球磨機研磨24小 時,則粉末顆粒之平均尺寸低於0. 4微米以下。繼之,將 粉末置在空氣中維持11 〇 〇 ~ 1 2 5 0 °C之條件.下乾燥並行煅燒 之。X -光繞射結杲顯示此方法可獲得所需,即根據本發明 之單相,且具有鈣鈦礦結構之摻雜型 材料。 第二種方法中,3份量之鈦酸四丁酯(TBT-Ti (CH4H90)4) 以及锆酸四丁 il(TBE-Zr(CH4Hg0)4)兩者分別以17份量之乾 燥(=無水)之異丙醇(C3 Η7 0 Η)稀釋之。兩種醇類混合物經過 攪拌三小時,同時避免與水接觸。根據所需之Ba/Zr比 值,將兩種溶液之部份混合再攪拌三小時,且避免與水接 觸。產生之混合物再以0 . 1 5 v 〇 1.之純(無水)醋酸 (CH3C00H)稀釋之。因此獲得之溶膠為水敏性,但在乾燥 氬氣之下亦可輕易地於室溫下保存超過一個月。 無水B a -錯酸Μ、C a -醋酸鹽、M u -醋酸H,庚I目酸錢以 及·^種或以上之元不Α之酸皇定置混合欣所萬之姐成3 醋酸鹽之混合物於醋酸以及水中(鹽/醋酸/水=1 / 8 / 7 )並 行攪拌以及加熱至漭點直到獲得清澈溶液為止。 繼之,將丨.0 01至丨.0 1 0莫耳之錯酸聲溶液與上述定比例 之溶勝混合之。最後授拌此混合场直到透光清激為止3再 將醋酸鹽-溶膠之混合物乾燥喷散以獲得凝膠粉末,緊接苐 Page 15 412762 V. Description of the invention CIO) 〇 〇 and Y b; A u e r-Re m y). The average grain size of the starting material is less than 1 micron3. Therefore, the obtained powder mixture is suspended in an aqueous solution, and a small amount of dispersant 1 is added to the suspension. The suspension is ground by a Zr02 ball mill for 24 hours. The average particle size of the powder is low. Below 0.4 microns. Next, the powder was dried in the air and maintained at a temperature of 11000 to 1250 ° C, and then calcined. X-ray diffraction scoliosis shows that this method achieves the desired, single-phase, doped material with perovskite structure according to the present invention. In the second method, 3 parts of tetrabutyl titanate (TBT-Ti (CH4H90) 4) and tetrabutyl zirconate (TBE-Zr (CH4Hg0) 4) are dried in 17 parts (= anhydrous). Dilute with isopropyl alcohol (C3 Η7 0 Η). The two alcohol mixtures were stirred for three hours while avoiding contact with water. According to the required Ba / Zr ratio, mix the two solution parts and stir for another three hours, avoiding contact with water. The resulting mixture was diluted with pure (anhydrous) acetic acid (CH3C00H) at 0.15 v 0.1. The sol obtained is therefore water sensitive, but can also be easily stored at room temperature for more than a month under dry argon. Anhydrous B a -acid M, C a -acetate, Mu -acetic acid H, heptanoate acid, and ^ or more kinds of acid of the non-A acid King set mixed Xinsuowan sister into 3 acetate The mixture was stirred in acetic acid and water (salt / acetic acid / water = 1/8/7) and heated to the boiling point until a clear solution was obtained. Then, 丨 .01 to 丨 .10 10 moles of acid solution is mixed with the above-mentioned fixed ratio solution. Finally, the mixing field is stirred until the light is transmitted. 3 The acetate-sol mixture is dried and dispersed to obtain a gel powder.
第16頁 412762 五、發明說明(11) 著再於空氣中維持丨0 5 0〜1 1 0 Ot下煆燒成一種徵晶粒之鈣 i太鑛型之混晶粉不3 煆燒後之鈣鈦礦材料(以苐一種或第二種方法取得)再以-相同之球磨機研磨約6小時。因而得到之粉末之平均顆抵 尺寸低於0. 8微米。將少量Si 02膠體以及黏結溶液(PVA)加 入此粉末中。繼之,由此粉末-黏結劑之混合物製出有厚 度,例如,4 0微来之綠色陶瓷薄膜。利用眾人知悉之技藝 將電極層以網版印刷法覆蓋於此等薄膜上。為了達成此目 的,採用了内含以N 1為主成份之金屬顆粒之網版印刷膏。 此種膏之金屬含量至少含有9 0 \v t % 1較佳為至少9 8 w t 之 N i 3此非燒結層之層厚約為2微罘。 繼之,將定尺寸之印成薄膜堆疊起來。堆疊此等薄膜之 方式係將偶數層與奇數層之電極層彼此稍微錯開。疊成之 薄膜則在高溫下(約8 0 °C )以單軸向高壓(約3 0 0巴)壓成一 種多層結構3本結構再經單向切成棒狀,另經苐二方向 (垂直於第一方向)切割以形成單一多層電容器單體=此等 單體係於韵和水之氮氣氣氛之含氬之還原氮氣下,約1 3 2 0 t條件下燒結。燒結後,所有單體在含02之氮氣氣氛中退 火約2小時(再氧化)。 最後,在多層電容器單韹之兩對置面利用浸塗法舖上外 接銅連線。此等連接係以可焊性NiSi合金利用賈凡尼強化 法完成之a接著測量此陶瓷多層電容器之機械以及電性。 許多實驗中顯示,以摻雜型之BaT 1 03為基質之系列多層 電容器係依上述論及之方法製成。不同系列之配方之主成.Page 16 412762 V. Description of the invention (11) Remaining in the air 丨 0 5 0 ~ 1 1 0 Ot sintered to form a kind of crystalline calcium i-type ore type mixed crystal powder not sintered after 3 sintered The perovskite material (obtained by the first method or the second method) is then ground with the same ball mill for about 6 hours. Therefore, the average particle size of the obtained powder was less than 0.8 microns. Add a small amount of Si 02 colloid and a binding solution (PVA) to this powder. Then, a green ceramic film having a thickness of, for example, 40 micrometers is produced from the powder-binder mixture. Electrode layers are screen-printed on these films using well-known techniques. To achieve this, a screen printing paste containing metal particles containing N 1 as a main component is used. The metal content of this paste contains at least 9 0 \ v t% 1 and preferably at least 9 8 w t of Ni 3. The thickness of this non-sintered layer is about 2 micrometers. Next, the sized printed films are stacked. The thin films are stacked in such a manner that the electrode layers of the even and odd layers are slightly staggered from each other. The laminated film is pressed into a multi-layer structure at a high temperature (about 80 ° C) with a uniaxial high pressure (about 300 bar). The structure is then cut into a rod shape in one direction, and the other direction Cut perpendicular to the first direction) to form a single multilayer capacitor cell = these single systems are sintered under a reducing nitrogen gas containing argon in a nitrogen atmosphere of rhyme and water under the condition of about 1320 t. After sintering, all monomers were annealed (reoxidized) in a nitrogen atmosphere containing 02 for about 2 hours. Finally, the two opposite sides of the single layer of the multilayer capacitor are coated with an external copper connection by dip coating. These connections are made of a solderable NiSi alloy using the Giovanni strengthening method. Then the mechanical and electrical properties of the ceramic multilayer capacitor are measured. Many experiments have shown that a series of multilayer capacitors with doped BaT 103 as the matrix are made according to the methods discussed above. Master of different series of recipes.
苐π頁 412762 五、發明說明(12) 份之組成為. 1 _ (Ba。. 9SCa〇.M)(Ti〇·81Zr。iSMn。(^Moq.〇025Y。.隨5)。.5 2- (Ba〇 96Ca〇, 04) (Ti 〇, 31Zr0_ I3Mn〇 005〇M〇0 〇〇25Y〇. 〇〇25)〇. 0995O3- 〇 3. (Ba0.邪Ca0. 04) (Ti0. 8025¾. isM% 〇〇5〇M〇〇. 〇〇5〇Y〇. 0075)0. 0990〇;3-5 4. (Ba0. g6CaM4) (Ti0.3IZr。. lsMn0. _Mo。. 0025H〇。, 0。5。)0. _q〇3— 5 5‘(Ba0.恥Ca0.04) (Ti0.slZrQ. lsMn0.005QM〇0.0025Zn0.0025)0. ¢99503-5 6. (Ba〇. g6Ca(].。4) (TiQ. 81Zr〇, lsMn。. 〇〇25Μ〇。. 〇。2和0. _)〇.。99〇〇3-5 7. (Ba0 96Ca〇_ 04) (Ti〇 8l^r0.18^n0. 0025^°0. 00'25J^0. 0050^0. 0990^3- 0 8. (Ba。g6Ca。04)(Ti0 slZr。18Mn。— ΰ025Μο0,0025Yb0 〇。50)。.哪。〇3—δ 此等系列中,測得之(平均)資料記錄如下:絕緣電阻 I R (在2 5 °C以及1 0 0 V條件下為1 09歐姆;1分鐘之後量測)、 居里溫度Tc ( °C ,分別在退火前後測量之),介電常數e以 及壽命(HALT環境中;1 40 t以及1 3V /微岽)。 ! no IR Tc £ HALT 1. 22 11.8/1.6 18200 >80 2. 4 27.9/18.9 19600 >80 η IS 7.5/1.5 16700 >80 4. 26 10.0/1.S 15900 >50 5. 11 15.5/-1.9 18400 >70 6. 7 19.3/17.1 22600 >70 7. 17 16.7/11.3 18600 >50 1 8. 10 14.2/-1.7 16600 >50苐 πPage 412762 5. The composition of the (12) part of the invention description is. 1 _ (Ba .. 9SCa〇.M) (Ti. 81Zr. ISMn. (^ Moq.〇025Y .. With 5) .. 5 2 -(Ba〇96Ca〇, 04) (Ti 〇, 31Zr0_ I3Mn〇005〇M〇0 〇〇25Y〇. 〇〇25) 〇 0995O3- 〇3. (Ba0. Evil Ca0. 04) (Ti0. 8025¾. isM% 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 〇 〇 3-0 (Ba0. g6CaM4) (Ti0.3IZr .. lsMn0. _Mo .. 0025H〇., 0 .5.) 0._q〇3--5 5 '(Ba0.sha Ca0.04) (Ti0.slZrQ.lsMn0.005QM〇0.0025Zn0.0025) 0. ¢ 99503-5 6. (Ba〇.g6Ca () 4) (TiQ. 81Zr0, lsMn: .0025M0 .. 2 and 0._) 0. 99.003-5 7. (Ba0 96Ca0_04) (Tio8l ^ r0.18 ^ n0. 0025 ^ ° 0. 00'25J ^ 0. 0050 ^ 0. 0990 ^ 3- 0 8. (Ba.g6Ca.04) (Ti0 slZr.18Mn.-ΰ025Mο0,0025Yb0 〇.50). Which. 〇3-—In these series, the measured (average) data is recorded as follows: Insulation resistance IR (1 09 ohms at 25 ° C and 100 V; measured after 1 minute), Curie temperature Tc (° C, measured before and after annealing), dielectric constant e and lifetime (HALT Environment; 1 40 t and 1 3V / μ /).! No IR Tc £ HALT 1. 22 11.8 / 1.6 18200 > 80 2. 4 27.9 / 18.9 19600 > 80 η IS 7.5 / 1.5 16700 > 80 4 . 26 10.0 / 1.S 15900 > 50 5. 11 15.5 / -1.9 18400 > 70 6. 7 19.3 / 17.1 22600 > 70 7. 17 16.7 / 11.3 18600 > 50 1 8. 10 14.2 / -1.7 16600 > 50
苐18頁苐 Page 18
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DE (1) | DE69832876T2 (en) |
TW (1) | TW412762B (en) |
WO (1) | WO1999018587A2 (en) |
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JP3087657B2 (en) * | 1996-07-26 | 2000-09-11 | 株式会社村田製作所 | Dielectric porcelain composition |
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1998
- 1998-09-21 JP JP52133699A patent/JP2001506425A/en active Pending
- 1998-09-21 EP EP98941634A patent/EP0988637B1/en not_active Expired - Lifetime
- 1998-09-21 DE DE69832876T patent/DE69832876T2/en not_active Expired - Fee Related
- 1998-09-21 WO PCT/IB1998/001448 patent/WO1999018587A2/en active IP Right Grant
- 1998-10-05 US US09/166,433 patent/US6072688A/en not_active Expired - Lifetime
- 1998-11-30 TW TW087119799A patent/TW412762B/en not_active IP Right Cessation
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102399083A (en) * | 2010-09-14 | 2012-04-04 | 中国钢铁股份有限公司 | Dielectric ceramic composition |
CN102399083B (en) * | 2010-09-14 | 2013-08-21 | 中国钢铁股份有限公司 | Dielectric ceramic composition |
CN107602114A (en) * | 2017-10-26 | 2018-01-19 | 贵州大学 | A kind of barium calcium zirconate titanate BCZT piezoelectric ceramics and its texturing preparation method |
CN107602114B (en) * | 2017-10-26 | 2022-05-20 | 贵州大学 | Barium calcium zirconate titanate BCZT piezoelectric ceramic and texturing preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
WO1999018587A2 (en) | 1999-04-15 |
JP2001506425A (en) | 2001-05-15 |
EP0988637A2 (en) | 2000-03-29 |
DE69832876D1 (en) | 2006-01-26 |
DE69832876T2 (en) | 2006-08-10 |
EP0988637B1 (en) | 2005-12-21 |
WO1999018587A3 (en) | 1999-06-17 |
US6072688A (en) | 2000-06-06 |
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